Dyeing process using a mixture obtained from an aerosol device comprising a glycerolated surfactant, and device therefor

ABSTRACT

The present invention relates to a process for dyeing keratin fibers in which a mixture is applied, this mixture being obtained from: ⋅a dye composition comprising at least one oxidation dye precursor, and ⋅an oxidizing composition comprising at least one chemical oxidizing agent, ⋅at least one of the compositions being dispensed from a pressurized container, ⋅the mixture of the two compositions comprising at least one saturated or unsaturated C 8 -C 40  fatty alcohol comprising from 1 to 10 mol of glycerol, preferably from 1 to 5 mol of glycerol and/or at least one oxyalkylenated carboxylic acid ether in acid or salified form, and also to a device suitable for performing this process.

CROSS REFERENCE TO RELATED APPLICATIONS

This is a national stage application of PCT/EP2013/058306, filedinternationally on Apr. 22, 2013, which claims priority to U.S.Provisional Application Nos. 61/663,162, and 61/663,172, both filed onJun. 22, 2012, as well as French Application Nos. 1253736 and 1253739,both filed Apr. 24, 2012, all of which are incorporated herein by theirentireties.

The present invention relates to a process for dyeing the hair using amixture comprising at least one glycerolated nonionic surfactant and/orat least one oxyalkylenated carboxylic acid ether surfactant, the saidmixture being obtained from two compositions, at least one of which isconditioned in a pressurized container, and also to a device suitablefor performing this process.

Among the methods for dyeing human keratin fibres, such as the hair,mention may be made of oxidation dyeing or permanent dyeing. Moreparticularly, this form of dyeing uses one or more oxidation dyes,usually one or more oxidation bases optionally combined with one or morecouplers.

In general, oxidation bases are chosen from ortho- orpara-phenylenediamines, ortho- or para-aminophenols and heterocycliccompounds. These oxidation bases are colourless or weakly colouredcompounds which, when combined with oxidizing products, can give accessto coloured entities.

Quite often, the shades obtained with these oxidation bases are variedby combining them with one or more couplers, these couplers being chosenespecially from aromatic meta-diamines, meta-aminophenols,meta-diphenols and certain heterocyclic compounds, such as indolecompounds.

The variety of the molecules used as oxidation bases and couplers allowsa wide range of colours to be obtained.

Permanent dyeing processes thus consist in using with the dyecomposition an aqueous composition comprising at least one oxidizingagent such as hydrogen peroxide, under alkaline pH conditions in thevast majority of cases. The alkaline agent conventionally used isaqueous ammonia or other alkaline agents, such as alkanolamines.

Dye compositions may take various forms such as lotions, gels,emulsions, creams or foams.

These compositions, in particular compositions comprising oxidationdyes, are obviously oxidation-sensitive and consequently containreducing agents or antioxidants. This oxidation-preventing action isalso reinforced by means of the inert atmosphere that is occasionallyused during the conditioning of these compositions.

The difficulty encountered with compositions of this type results,precisely, from their oxidation sensitivity. Specifically, during theiruse, they come into contact with atmospheric oxygen, which thus obligesthem to be used quickly. If this is not done, the compositions becomeunusable after storage and are lost.

Compositions which are conditioned in pressurized containers that canprevent the composition from coming into contact with air during theiruse are known in the field of hair dyeing, as is described, for example,in US 2010/0236570 or FR2048629.

However, the coverage of the hair, in particular of grey hair, stillremains to be improved, as does the galenical quality of the productobtained from the pressurized container.

There is an ongoing need to develop oxidation dye compositions, inparticular in foam form, which are easy to prepare and to apply andwhich remain sufficiently stable over time, while at the same timemaintaining efficient dyeing properties, especially in terms of coverageof the hair, more particularly of grey hair, but also in terms of theintensity, homogeneity and chromaticity of the coloration obtained.

This aim and others are achieved by the present invention, one subjectof which is a process for dyeing keratin fibres in which a mixture isapplied to the said fibres, this mixture being obtained from:

-   -   a dye composition comprising at least one oxidation dye        precursor, and    -   an oxidizing composition comprising at least one chemical        oxidizing agent,    -   at least one of the compositions being dispensed from a        pressurized device,    -   the mixture of the two compositions comprising at least one        saturated or unsaturated C₈-C₄₀ fatty alcohol comprising from 1        to 10 mol of glycerol, preferably from 1 to 5 mol of glycerol        and/or at least one oxyalkylenated carboxylic acid ether in acid        or salified form

The invention also relates to a device that is suitable for performingthe process according to the invention, comprising:

-   -   a first container containing a dye composition comprising at        least one oxidation dye precursor, and    -   a second container containing an oxidizing composition        comprising at least one chemical oxidizing agent,    -   at least one of the two containers being pressurized, and        preferably both the containers being pressurized;    -   a means for dispensing the compositions;    -   the mixture of the two compositions comprising at least one        saturated or unsaturated C₈-C₄₀ fatty alcohol comprising from 1        to 10 mol of glycerol, preferably from 1 to 5 mol of glycerol        and/or at least one oxyalkylenated carboxylic acid ether in acid        or salified form.

Preferably, the composition used in the process according to theinvention is in the form of a foam that is particularly pleasant toapply.

It has a light, airy texture, which makes it particularly pleasant touse. The qualities of the foam are sufficiently long-lasting to enableuniform application of the dye product, without running.

The composition of the invention makes it possible to retain dyeingproperties, such as strength of the colour, resistance to externalagents (shampooing, perspiration, light) and selectivity, and mostparticularly coverage of grey hair.

Other characteristics and advantages of the invention will emerge moreclearly on reading the description and the examples that follow.

In the text hereinbelow, and unless otherwise indicated, the limits of arange of values are included in that range. The term “at least one”associated with an ingredient of the composition means “one or more”.

The terms “oxyalkylenated”, “oxyethylenated”, “oxypropylenated” and“glycerolated” cover, respectively, mono- or poly-oxyalkylenated,oxyethylenated, oxypropylenated or glycerolated compounds, unlessotherwise mentioned.

Unless otherwise indicated, the contents of the ingredients present inthe compositions are indicated without taking into account the contentof propellant gas(es).

The human keratin fibres treated via the process according to theinvention are preferably the hair.

Mono- or Polyqlycerolated Fatty Alcohol Surfactant

As indicated previously, the mixture used in the process according tothe invention may comprise at least one saturated or unsaturated C₈-C₄₀fatty alcohol comprising from 1 to 10 mol of glycerol and preferablyfrom 1 to 5 mol of glycerol.

In particular, the mono- or polyglycerolated C₈-C₄₀ alcohols correspondto formula (A) below:R₁O—[CH₂—CH(CH₂OH)—O]_(m)—H  (A)

in which formula:

-   -   R₁ represents a linear or branched C₈-C₄₀ and preferably C₈-C₃₀        alkyl or alkenyl radical; and    -   m represents a number ranging from 1 to 30 and preferably from 1        to 10.

As examples of compounds of formula (A) that are suitable in the contextof the invention, mention may be made of lauryl alcohol containing 4 molof glycerol (INCI name: Polyglyceryl-4 Lauryl Ether), lauryl alcoholcontaining 1.5 mol of glycerol, oleyl alcohol containing 4 mol ofglycerol (INCI name: Polyglyceryl-4 Oleyl Ether), oleyl alcoholcontaining 2 mol of glycerol (INCI name: Polyglyceryl-2 oleyl Ether),cetearyl alcohol containing 2 mol of glycerol, cetearyl alcoholcontaining 6 mol of glycerol, oleocetyl alcohol containing 6 mol ofglycerol and octadecanol containing 6 mol of glycerol.

The alcohol of formula (A) may represent a mixture of alcohols in thesame way that the value of m represents a statistical value, which meansthat several species of polyglycerolated fatty alcohols may coexist inthe form of a mixture in a commercial product.

Among the mono- or polyglycerolated alcohols, it is more particularlypreferred to use the C₈/C₁₀ alcohol containing 1 mol of glycerol, theC₁₀/C₁₂ alcohol containing 1 mol of glycerol and the C₁₂ alcoholcontaining 1.5 mol of glycerol.

According to a preferred embodiment of the invention, the content ofmono- or polyglycerolated surfactant(s) represents from 0.1% to 50% byweight, preferably from 1% to 20% by weight and even more particularlyfrom 5% to 15% by weight relative to the weight of the mixture.

The mono- or polyglycerolated fatty alcohol surfactant(s) may be in thedye composition, in the oxidizing composition or in both compositionssimultaneously.

Oxyalkylenated Carboxylic Acid Ether

As indicated previously, the mixture used in the context of theinvention may comprise at least one oxyalkylenated carboxylic acidether, in acid or salified form.

More particularly, the oxyalkylenated carboxylic acid ether(s)correspond to the following formula:

in which:

-   -   R represents a linear or branched C₈-C₂₂ alkyl or alkenyl or a        (C₈-C₉)alkylphenyl radical or mixture of radicals,    -   n is an integer or decimal number ranging from 2 to 24,    -   p is an integer or decimal number ranging from 0 to 6,    -   A denotes a hydrogen atom, an ammonium ion or an ion derived        from an alkali metal or an alkaline-earth metal (for example Na,        K, Li or Mg) or an ion derived from an organic amine such as        monoethanolamine or triethanolamine.

Preferably, the oxyalkylenated carboxylic acid ether(s) are chosen fromthose of formula (I) in which R denotes a (C₁₂-C₁₄)alkyl, oleyl, cetylor stearyl radical or mixture of radicals; a nonylphenyl or octylphenylradical, A denotes a hydrogen atom or a sodium ion, p=0, and n rangesfrom 2 to 20 and preferably from 2 to 10.

The oxyalkylenated carboxylic acid ether(s) are preferably chosen fromthose of formula (I) in which R denotes an alkyl radical (C₁₂), Adenotes a hydrogen atom or a sodium ion, p=0 and n ranges from 2 to 10.

According to a preferred embodiment of the invention, the content ofoxyalkylenated carboxylic acid ether(s), in acid or salified form,represents from 0.1% to 40% by weight and preferably from 1% to 10% byweight, relative to the weight of the mixture.

The oxyalkylenated carboxylic acid ether(s) may be in the dyecomposition, in the oxidizing composition or in both compositionssimultaneously.

Dye Composition

Dyes

The dye composition used in the process according to the inventioncomprises at least one oxidation dye precursor.

Oxidation bases and couplers may be used as oxidation dye precursors.

By way of example, the oxidation bases are chosen frompara-phenylenediamines, bis(phenyl)alkylenediamines, para-aminophenols,ortho-aminophenols and heterocyclic bases, and the addition saltsthereof.

Among the para-phenylenediamines that may be mentioned, for example, arepara-phenylenediamine, para-toluenediamine,2-chloro-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine,2,6-dimethyl-para-phenylenediamine, 2,6-diethyl-para-phenylenediamine,2,5-dimethyl-para-phenylenediamine, N,N-dimethyl-para-phenylenediamine,N,N-diethyl-para-phenylenediamine, N,N-dipropyl-para-phenylenediamine,4-amino-N,N-diethyl-3-methylaniline,N,N-bis(-hydroxyethyl)-para-phenylenediamine,4-N,N-bis(-hydroxyethyl)amino-2-methylaniline,4-N,N-bis(-hydroxyethyl)amino-2-chloroaniline,2-hydroxyethyl-para-phenylenediamine, 2-fluoro-para-phenylenediamine,2-isopropyl-para-phenylenediamine,N-(β-hydroxypropyl)-para-phenylenediamine,2-hydroxymethyl-para-phenylenediamine,N,N-dimethyl-3-methyl-para-phenylenediamine,N-ethyl-N-(-hydroxyethyl)-para-phenylenediamine,N-(,y-dihydroxypropyl)-para-phenylenediamine,N-(4′-aminophenyl)-para-phenylenediamine,N-phenyl-para-phenylenediamine,2-n-hydroxyethyloxy-para-phenylenediamine,2-acetylaminoethyloxy-para-phenylenediamine,N-(-methoxyethyl)-para-phenylenediamine, 4-aminophenylpyrrolidine,2-thienyl-para-phenylenediamine, 2-p-hydroxyethylamino-5-aminotolueneand 3-hydroxy-1-(4′-aminophenyl)pyrrolidine, and the addition saltsthereof with an acid. Among the para-phenylenediamines mentioned above,para-phenylenediamine, para-toluenediamine,2-isopropyl-para-phenylenediamine,2-p-hydroxyethyl-para-phenylenediamine,2-hydroxyethyloxy-para-phenylenediamine,2,6-dimethyl-para-phenylenediamine, 2,6-diethyl-para-phenylenediamine,2,3-dimethyl-para-phenylenediamine,N,N-bis(-hydroxyethyl)-para-phenylenediamine,2-chloro-para-phenylenediamine and2-p-acetylaminoethyloxy-para-phenylenediamine, and the addition saltsthereof with an acid, are particularly preferred.

Among the para-phenylenediamines mentioned above, para-phenylenediamine,para-tolylenediamine, 2-isopropyl-para-phenylenediamine,2-β-hydroxyethyl-para-phenylenediamine,2-β-hydroxyethyloxy-para-phenylenediamine,2,6-dimethyl-para-phenylenediamine, 2,6-diethyl-para-phenylenediamine,2,3-dimethyl-para-phenylenediamine,N,N-bis(β-hydroxyethyl)-para-phenylenediamine,2-chloro-para-phenylenediamine and2-β-acetylaminoethyloxy-para-phenylenediamine, and the addition saltsthereof with an acid, are particularly preferred.

Among the bis(phenyl)alkylenediamines that may be mentioned, forexample, areN,N′-bis(β-hydroxyethyl)-N,N′-bis(4′-aminophenyl)-1,3-diaminopropanol,N,N′-bis(β-hydroxyethyl)-N,N′-bis(4′-aminophenyl)ethylenediamine,N,N′-bis(4-aminophenyl)tetramethylenediamine,N,N′-bis(β-hydroxyethyl)-N,N′-bis(4-aminophenyl)tetramethylenediamine,N,N′-bis(4-methylaminophenyl)tetramethylenediamine,N,N′-bis(ethyl)-N,N′-bis(4′-amino-3′-methylphenyl)ethylenediamine,1,8-bis(2,5-diaminophenoxy)-3,6-dioxaoctane and the addition saltsthereof.

Among the para-aminophenols that may be mentioned, for example, arepara-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol,4-amino-3-chlorophenol, 4-amino-3-hydroxymethylphenol,4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol,4-amino-2-methoxymethylphenol, 4-amino-2-aminomethylphenol,4-amino-2-(β-hydroxyethylaminomethyl)phenol and 4-amino-2-fluorophenol,and the addition salts thereof with an acid.

Among the ortho-aminophenols that may be mentioned, for example, are2-aminophenol, 2-amino-5-methylphenol, 2-amino-6-methylphenol and5-acetamido-2-aminophenol, and the addition salts thereof.

Among the heterocyclic bases that may be mentioned, for example, arepyridine derivatives, pyrimidine derivatives and pyrazole derivatives.

Among the pyridine derivatives that may be mentioned are the compoundsdescribed, for example, in patents GB 1 026 978 and GB 1 153 196, forinstance 2,5-diaminopyridine, 2-(4-methoxyphenyl)amino-3-aminopyridineand 3,4-diaminopyridine, and the addition salts thereof.

Other pyridine oxidation bases that are useful in the present inventionare the 3-aminopyrazolo[1,5-a]pyridine oxidation bases or the additionsalts thereof described, for example, in patent application FR 2 801308. Mention may be made, by way of example, ofpyrazolo[1,5-a]pyrid-3-ylamine,2-(acetylamino)pyrazolo[1,5-a]pyrid-3-ylamine,2-(morpholin-4-yl)pyrazolo[1,5-a]pyrid-3-ylamine,3-aminopyrazolo[1,5-a]pyridine-2-carboxylic acid,2-methoxypyrazolo[1,5-a]pyrid-3-ylamine,(3-aminopyrazolo[1,5-a]pyrid-7-yl)methanol,2-(3-aminopyrazolo[1,5-a]pyrid-5-yl)ethanol,2-(3-aminopyrazolo[1,5-a]pyrid-7-yl)ethanol,(3-aminopyrazolo[1,5-a]pyrid-2-yl)methanol,3,6-diaminopyrazolo[1,5-a]pyridine, 3,4-diaminopyrazolo[1,5-a]pyridine,pyrazolo[1,5-a]pyridine-3,7-diamine,7-(morpholin-4-yl)pyrazolo[1,5-a]pyrid-3-ylamine,pyrazolo[1,5-a]pyridine-3,5-diamine,5-(morpholin-4-yl)pyrazolo[1,5-a]pyrid-3-ylamine,2-[(3-aminopyrazolo[1,5-a]pyrid-5-yl)(2-hydroxyethyl)amino]ethanol,2-[(3-aminopyrazolo[1,5-a]pyrid-7-yl)(2-hydroxyethyl)amino]ethanol,3-aminopyrazolo[1,5-a]pyridin-5-ol, 3-aminopyrazolo[1,5-a]pyridin-4-ol,3-aminopyrazolo[1,5-a]pyridin-6-ol, 3-aminopyrazolo[1,5-a]pyridin-7-oland the addition salts thereof.

Among the pyrimidine derivatives that may be mentioned are the compoundsdescribed, for example, in patents DE 2359399, JP 88-169571, JP 05-63124and EP 0 770 375 or patent application WO 96/15765, such as2,4,5,6-tetraaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine,2-hydroxy-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine,2,5,6-triaminopyrimidine and addition salts thereof, and tautomericforms thereof, when a tautomeric equilibrium exists.

Among the pyrazole derivatives that may be mentioned are the compoundsdescribed in patents DE 3843892, DE 4133957 and patent applications WO94/08969, WO 94/08970, FR-A-2 733 749 and DE 195 43 988, such as4,5-diamino-1-methylpyrazole, 4,5-diamino-1-(β-hydroxyethyl)pyrazole,3,4-diaminopyrazole, 4,5-diamino-1-(4′-chlorobenzyl)pyrazole,4,5-diamino-1,3-dimethylpyrazole, 4,5-diamino-3-methyl-1-phenylpyrazole,4,5-diamino-1-methyl-3-phenylpyrazole,4-amino-1,3-dimethyl-5-hydrazinopyrazole,1-benzyl-4,5-diamino-3-methylpyrazole,4,5-diamino-3-tert-butyl-1-methylpyrazole,4,5-diamino-1-tert-butyl-3-methylpyrazole,4,5-diamino-1-(β-hydroxyethyl)-3-methylpyrazole,4,5-diamino-1-ethyl-3-methylpyrazole,4,5-diamino-1-ethyl-3-(4′-methoxyphenyl)pyrazole,4,5-diamino-1-ethyl-3-hydroxymethylpyrazole,4,5-diamino-3-hydroxymethyl-1-methylpyrazole,4,5-diamino-3-hydroxymethyl-1-isopropylpyrazole,4,5-diamino-3-methyl-1-isopropylpyrazole,4-amino-5-(2′-aminoethyl)amino-1,3-dimethylpyrazole,3,4,5-triamino-pyrazole, 1-methyl-3,4,5-triaminopyrazole,3,5-diamino-1-methyl-4-methylaminopyrazole,3,5-diamino-4-(β-hydroxyethyl)amino-1-methylpyrazole, and addition saltsthereof. Use may also be made of 4,5-diamino-1-(β-methoxyethyl)pyrazole.

A 4,5-diaminopyrazole will preferably be used, and even morepreferentially 4,5-diamino-1-(β-hydroxyethyl)pyrazole and/or a saltthereof.

Pyrazole derivatives that may also be mentioned includediamino-N,N-dihydropyrazolopyrazolones and especially those described inpatent application FR-A-2 886 136, such as the following compounds andthe addition salts thereof:2,3-diamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one,2-amino-3-ethylamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one,2-amino-3-isopropylamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one,2-amino-3-(pyrrolidin-1-yl)-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one,4,5-diamino-1,2-dimethyl-1,2-dihydropyrazol-3-one,4,5-diamino-1,2-diethyl-1,2-dihydropyrazol-3-one,4,5-diamino-1,2-di(2-hydroxyethyl)-1,2-dihydropyrazol-3-one,2-amino-3-(2-hydroxyethyl)amino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one,2-amino-3-dimethylamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one,2,3-diamino-5,6,7,8-tetrahydro-1H,6H-pyridazino[1,2-a]pyrazol-1-one,4-amino-1,2-diethyl-5-(pyrrolidin-1-yl)-1,2-dihydropyrazol-3-one,4-amino-5-(3-dimethylaminopyrrolidin-1-yl)-1,2-diethyl-1,2-dihydropyrazol-3-one,2,3-diamino-6-hydroxy-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one.2,3-Diamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one and/or a saltthereof will preferably be used.

Use will preferably be made, as heterocyclic bases, of4,5-diamino-1-(β-hydroxyethyl)pyrazole and/or2,3-diamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one and/or a saltthereof.

Among the couplers that may be used in the composition used in theprocess according to the invention, mention may be made especially ofmeta-phenylenediamines, meta-aminophenols, meta-diphenols,naphthalene-based couplers, heterocyclic couplers, for instance indolederivatives, indoline derivatives, sesamol and derivatives thereof,pyridine derivatives, pyrazolotriazole derivatives, pyrazolones,indazoles, benzimidazoles, benzothiazoles, benzoxazoles,1,3-benzodioxoles and quinolines, and the addition salts of thesecompounds with an acid.

These couplers are more particularly chosen from2,4-diamino-1-(β-hydroxyethyloxy)benzene, 2-methyl-5-aminophenol,5-N-(β-hydroxyethyl)amino-2-methylphenol, 3-aminophenol,1,3-dihydroxybenzene, 1,3-dihydroxy-2-methylbenzene,4-chloro-1,3-dihydroxybenzene,2-amino-4-(β-hydroxyethylamino)-1-methoxybenzene, 1,3-diaminobenzene,1,3-bis(2,4-diaminophenoxy)propane, sesamol,1-amino-2-methoxy-4,5-methylenedioxybenzene, α-naphthol,6-hydroxyindole, 4-hydroxyindole, 4-hydroxy-N-methylindole,6-hydroxyindoline, 2,6-dihydroxy-4-methylpyridine,1H-3-methylpyrazol-5-one, 1-phenyl-3-methylpyrazol-5-one,2-amino-3-hydroxypyridine, 3,6-dimethylpyrazolo[3,2-c]-1,2,4-triazoleand 2,6-dimethylpyrazolo[1,5-b]-1,2,4-triazole, the addition saltsthereof with an acid, and mixtures thereof.

The addition salts of the oxidation bases and couplers are especiallychosen from the addition salts with an acid such as the hydrochlorides,hydrobromides, sulfates, citrates, succinates, tartrates, lactates,tosylates, benzenesulfonates, phosphates and acetates.

The oxidation base(s) are each generally present in an amount of from0.0001% to 10% by weight relative to the total weight of thecomposition, and preferably from 0.005% to 5% by weight relative to thetotal weight of the dye composition.

The coupler(s) each generally represent from 0.0001% to 10% by weightrelative to the total weight of the composition, and preferably from0.005% to 5% by weight relative to the total weight of the dyecomposition.

The dye composition used in the process according to the invention maycontain synthetic or natural, cationic or nonionic, direct dyes.

Examples of particularly suitable direct dyes that may be mentionedinclude nitrobenzene dyes; azo direct dyes; azomethine direct dyes;methine direct dyes; azacarbocyanin direct dyes, for instancetetraazacarbocyanins (tetraazapentamethines); quinone and in particularanthraquinone, naphthoquinone or benzoquinone direct dyes; azine directdyes; xanthene direct dyes; triarylmethane direct dyes; indoamine directdyes; indigoid direct dyes; phthalocyanin direct dyes, porphyrin directdyes and natural direct dyes, alone or as mixtures. In particular,mention may be made of direct dyes from among: azo; methine; carbonyl;azine; nitro (hetero)aryl; tri(hetero)arylmethane; porphyrin;phthalocyanine and natural direct dyes, alone or as mixtures.

When they are present, the direct dye(s) more particularly representfrom 0.0001% to 10% by weight and preferably from 0.005% to 5% by weightrelative to the total weight of the dye composition.

Alkaline Agent

According to a preferred variant of the invention, the dye compositioncomprises at least one alkaline agent.

This agent may be chosen from mineral or organic or hybrid alkalineagents, or mixtures thereof.

The mineral alkaline agent(s) are preferably chosen from aqueousammonia, alkali carbonates or bicarbonates such as sodium or potassiumcarbonates and sodium or potassium bicarbonates, sodium hydroxide orpotassium hydroxide, or mixtures thereof.

The organic alkaline agent(s) are preferably chosen from organic amineswith a pK_(b) at 25° C. of less than 12, preferably less than 10 andeven more advantageously less than 6. It should be noted that it is thepK_(b) corresponding to the function of highest basicity.

Mention may be made, as hybrid compounds, of the salts of theabovementioned amines with acids, such as carbonic acid or hydrochloricacid.

The organic alkaline agent(s) are chosen, for example, fromalkanolamines, oxyethylenated and/or oxypropylenated ethylenediamines,amino acids and the compounds having the following formula:

in which W is a C₁-C₆ alkylene residue optionally substituted with ahydroxyl group or a C₁-C₆ alkyl radical; Rx, Ry, Rz and Rt, which may beidentical or different, represent a hydrogen atom or a C₁-C₆ alkyl,C₁-C₆ hydroxyalkyl or C₁-C₆ aminoalkyl radical.

Examples of such amines that may be mentioned include1,3-diaminopropane, 1,3-diamino-2-propanol, spermine and spermidine.

The term “alkanolamine” means an organic amine comprising a primary,secondary or tertiary amine function, and one or more linear or branchedC₁-C₈ alkyl groups bearing one or more hydroxyl radicals.

Alkanolamines such as monoalkanolamines, dialkanolamines ortrialkanolamines comprising from one to three identical or differentC₁-C₄ hydroxyalkyl radicals are in particular suitable for performingthe invention.

Among compounds of this type, mention may be made of monoethanolamine,diethanolamine, triethanolamine, monoisopropanolamine,diisopropanolamine, N-dimethylaminoethanolamine,2-amino-2-methyl-1-propanol, triisopropanolamine,2-amino-2-methyl-1,3-propanediol, 3-amino-1,2-propanediol,3-dimethylamino-1,2-propanediol and tris(hydroxymethylamino)methane.

More particularly, the amino acids that may be used are of natural orsynthetic origin, in their L, D or racemic form, and comprise at leastone acid function more particularly chosen from carboxylic acid,sulfonic acid, phosphonic acid and phosphoric acid functions. The aminoacids can be in the neutral or ionic form.

Mention may in particular be made, as amino acids which can be used inthe present invention, of aspartic acid, glutamic acid, alanine,arginine, ornithine, citrulline, asparagine, carnitine, cysteine,glutamine, glycine, histidine, lysine, isoleucine, leucine, methionine,N-phenylalanine, proline, serine, taurine, threonine, tryptophan,tyrosine and valine.

Advantageously, the amino acids are basic amino acids comprising anadditional amine function optionally included in a ring or in a ureidofunction.

Such basic amino acids are preferably chosen from those corresponding tothe following formula:

in which R denotes a group chosen from:

The compounds corresponding to the above formula are histidine, lysine,arginine, ornithine and citrulline.

The organic amine may also be chosen from organic amines of heterocyclictype. Besides histidine that has already been mentioned in the aminoacids, mention may be made in particular of pyridine, piperidine,imidazole, triazole, tetrazole and benzimidazole.

The organic amine can also be chosen from amino acid dipeptides. Asamino acid dipeptides that may be used in the present invention, mentionmay be made especially of carnosine, anserine and balenine.

The organic amine is chosen from compounds comprising a guanidinefunction. As amines of this type that may be used in the presentinvention, besides arginine, which has already been mentioned as anamino acid, mention may be made especially of creatine, creatinine,1,1-dimethylguanidine, 1,1-diethylguanidine, glycocyamine, metformin,agmatine, N-amidinoalanine, 3-guanidinopropionic acid,4-guanidinobutyric acid and2-([amino(imino)methyl]amino)ethane-1-sulfonic acid.

Mention may be made in particular of guanidine carbonate ormonoethanolamine hydrochloride as hybrid compounds.

More particularly, the composition of the invention contains, asalkaline agent, aqueous ammonia and/or at least one alkanolamine and/orat least one basic amino acid, more advantageously aqueous ammoniaand/or at least one alkanolamine. Preferably, the alkaline agent ischosen from aqueous ammonia and monoethanolamine, or a mixture thereof.

Advantageously, the dye composition has a content of alkaline agent(s)ranging from 0.01% to 30% by weight, preferably from 0.1% to 20% byweight and better still from 1% to 10% by weight relative to the weightof the said dye composition. It should be noted that this content isexpressed as NH₃ in the case where the alkaline agent is aqueousammonia.

Additional Surfactants

The dye composition may also comprise one or more additional surfactantsother than the abovementioned mono- or polyglycerolated fatty alcoholsurfactant(s) and oxyalkylenated carboxylic acid ether in acid orsalified form.

In particular, the additional surfactant(s) are chosen from anionicother than the oxyalkylenated carboxylic acid ether in acid or salifiedform, amphoteric, zwitterionic, cationic and nonionic surfactants otherthan the said mono- or polyglycerolated fatty alcohols, andpreferentially nonionic surfactants.

The term “anionic surfactant” means a surfactant comprising, as ionic orionizable groups, only anionic groups. These anionic groups arepreferably chosen from the groups —C(O)OH, —C(O)O—, —SO₃H, —S(O)₂O—,—OS(O)₂OH, —OS(O)₂O—, —P(O)OH₂, —P(O)₂O—, —P(O)C₂—, —P(OH)₂, ═P(O)OH,—P(OH)O—, ═P(O)O—, ═POH and ═PO—, the anionic parts comprising acationic counterion such as an alkali metal, an alkaline-earth metal oran ammonium.

As examples of anionic surfactants that may be used in the dyecomposition, mention may be made of alkyl sulfates, alkyl ethersulfates, alkylamido ether sulfates, alkylarylpolyether sulfates,monoglyceride sulfates, alkylsulfonates, alkylamidesulfonates,alkylarylsulfonates, α-olefin sulfonates, paraffin sulfonates,alkylsulfosuccinates, alkylether sulfosuccinates, alkylamidesulfosuccinates, alkylsulfoacetates, acylsarcosinates, acylglutamates,alkylsulfosuccinamates, acylisethionates and N-acyltaurates, salts ofalkyl monoesters of polyglycoside-polycarboxylic acids, acyllactylates,D-galactoside uronic acid salts, alkylaryl ether carboxylic acid salts,alkylamido ether carboxylic acid salts, and the correspondingnon-salified forms of all these compounds, the alkyl and acyl groups ofall these compounds comprising from 6 to 40 carbon atoms and the arylgroup denoting a phenyl group.

These compounds can be oxyethylenated and then preferably comprise from1 to 50 ethylene oxide units.

The salts of C₆-C₂₄ alkyl monoesters of polyglycoside-polycarboxylicacids can be chosen from C₆-C₂₄ alkyl polyglycoside-citrates, C₆-C₂₄alkyl polyglycoside-tartrates and C₆-C₂₄ alkylpolyglycoside-sulfosuccinates.

When the anionic surfactant(s) are in salt form, they may be chosen fromalkali metal salts such as sodium or potassium salt and preferablysodium salt, ammonium salts, amine salts and in particular amino alcoholsalts or alkaline-earth metal salts such as magnesium salts.

Examples of amino alcohol salts that may especially be mentioned includemonoethanolamine, diethanolamine and triethanolamine salts,monoisopropanolamine, diisopropanolamine or triisopropanolamine salts,2-amino-2-methyl-1-propanol salts, 2-amino-2-methyl-1,3-propanediolsalts and tris(hydroxymethyl)aminomethane salts.

Alkali metal or alkaline-earth metal salts, and in particular sodium ormagnesium salts, are preferably used.

Use is preferably made, among the anionic surfactants mentioned, of(C₆-C₂₄)alkyl sulfates, (C₆-C₂₄)alkyl ether sulfates comprising from 2to 50 ethylene oxide units, in particular in the form of alkali metal,ammonium, amino alcohol and alkaline-earth metal salts, or a mixture ofthese compounds.

In particular, it is preferable to use (C₁₂-C₂₀)alkyl sulfates,(C₁₂-C₂₀)alkyl ether sulfates comprising from 2 to 20 ethylene oxideunits, in particular in the form of alkali metal, ammonium, aminoalcohol and alkaline-earth metal salts, or a mixture of these compounds.Better still, it is preferred to use sodium lauryl ether sulfatecontaining 2.2 mol of ethylene oxide.

The amphoteric or zwitterionic surfactant(s), which are preferably (a)non-silicone surfactant(s), which can be used in the present inventionmay in particular be derivatives of optionally quaternized secondary ortertiary aliphatic amines, in which derivatives the aliphatic group is alinear or branched chain comprising from 8 to 22 carbon atoms, the saidamine derivatives comprising at least one anionic group, such as, forexample, a carboxylate, sulfonate, sulfate, phosphate or phosphonategroup. Mention may be made in particular of (C₈-C₂₀)alkylbetaines,sulfobetaines, (C₈-C₂₀)alkylamido(C₃-C₈)alkylbetaines and(C₈-C₂₀)alkylamido(C₆-C₈)alkylsulfobetaines.

Among the optionally quaternized secondary or tertiary aliphatic aminederivatives that may be used, as defined above, mention may also be madeof the compounds having the respective structures (B1) and (B2) below:R_(a)—C(O)—NH—CH₂—CH₂—N⁺(R_(b))(R_(c))—CH₂C(O)O⁻,M⁺,X⁻  (B1)

in which formula:

-   -   R_(a) represents a C₁₀-C₃₀ alkyl or alkenyl group derived from        an acid R_(a)—COOH preferably present in hydrolysed coconut oil,        or a heptyl, nonyl or undecyl group;    -   R_(b) represents a β-hydroxyethyl group; and    -   R_(c) represents a carboxymethyl group;    -   M⁺ represents a cationic counterion derived from an alkali metal        or alkaline-earth metal, such as sodium, an ammonium ion or an        ion derived from an organic amine; and    -   X⁻ represents an organic or inorganic anionic counterion, such        as that chosen from halides, acetates, phosphates, nitrates,        (C₁-C₄)alkyl sulfates, (C₁-C₄)alkyl- or        (C₁-C₄)alkylarylsulfonates, in particular methyl sulfate and        ethyl sulfate; or alternatively M⁺ and X⁻ are absent;        R_(a′)—C(O)—NH—CH₂—CH₂—N(B)(B′)  (B2)

in which formula:

-   -   B represents the group —CH₂—CH₂—O—X′;    -   B′ represents the group —(CH₂)_(z)Y′, with z=1 or 2;    -   X′ represents the group —CH₂—C(O)OH, —CH₂—C(O)OZ′,        —CH₂—CH₂—C(O)OH, —CH₂—CH₂—C(O)OZ′, or a hydrogen atom;    -   Y′ represents the group —C(O)OH, —C(O)OZ′, —CH₂—CH(OH)—SO₃H or        the group —CH₂—CH(OH)—SO₃—Z′;    -   Z′ represents a cationic counterion derived from an alkali metal        or alkaline-earth metal, such as sodium, an ammonium ion or an        ion derived from an organic amine;    -   R_(a′) represents a C₁₀-C₃₀ alkyl or alkenyl group of an acid        R_(a′)—C(O)OH preferably present in coconut oil or in hydrolysed        linseed oil, an alkyl group, especially of C₁₇ and its iso form,        or an unsaturated C₁₇ group.

These compounds of formula (B1) or (B2) are classified in the CTFAdictionary, 5th edition, 1993, under the names disodiumcocoamphodiacetate, disodium lauroamphodiacetate, disodiumcaprylamphodiacetate, disodium capryloamphodiacetate, disodiumcocoamphodipropionate, disodium lauroamphodipropionate, disodiumcaprylamphodipropionate, disodium capryloamphodipropionate,lauroamphodipropionic acid and cocoamphodipropionic acid.

By way of example, mention may be made of the cocoamphodiacetate sold bythe company Rhodia under the trade name Miranol® C2M Concentrate.

Among the amphoteric or zwitterionic surfactants mentioned above, use ispreferably made of (C₈-C₂₀)alkylbetaines such as cocoylbetaine, (C₈-C₂₀)alkylamido(C₃-C₈)alkylbetaines such as cocamidopropylbetaine, andmixtures thereof. More preferentially, the amphoteric or zwitterionicsurfactant(s) are chosen from cocamidopropylbetaine and cocoylbetaine.

Use may also be made of compounds of formula (B′2):R_(a″)—NH—CH(Y″)—(CH₂)n-C(O)—NH—(CH₂)n′-N(R_(d))(R_(e))  (B′2)

in which formula:

-   -   Y″ represents the group —C(O)OH, —C(O)OZ″, —CH₂—CH(OH)—SO₃H or        the group —CH₂—CH(OH)—SO₃—Z″;    -   R_(d) and R_(e), independently of each other, represent a C₁-C₄        alkyl or hydroxyalkyl radical;    -   Z″ represents a cationic counterion derived from an alkali metal        or alkaline-earth metal, such as sodium, an ammonium ion or an        ion derived from an organic amine;    -   R_(a″) represents a C₁₀-C₃₀ alkyl or alkenyl group of an acid        R_(a″)C(O)OH preferably present in coconut oil or in hydrolysed        linseed oil.    -   n and n′ denote, independently of each other, an integer ranging        from 1 to 3.

Among the compounds of formula (B′2), mention may be made of thecompound classified in the CTFA dictionary under the name sodiumdiethylaminopropyl cocoaspartamide and sold by the company Chimex underthe name Chimexane HB.

Among the amphoteric or zwitterionic surfactants mentioned above, use ispreferably made of (C₈-C₂₀)alkylbetaines such as cocoylbetaine,(C₈-C₂₀)alkylamido(C₃-C₈)alkylbetaines such as cocoylamidopropylbetaine,and the compounds of formula (B′2) such as the sodium salt ofdiethylaminopropyl laurylaminosuccinamate (INCI name: sodiumdiethylaminopropyl cocoaspartamide), and mixtures thereof.

The cationic surfactant(s) that may be used in the dye compositioncomprise, for example, salts of optionally polyoxyalkylenated primary,secondary or tertiary fatty amines, quaternary ammonium salts, andmixtures thereof.

Examples of quaternary ammonium salts that may especially be mentionedinclude:

-   those corresponding to the general formula (B3) below:

in which formula:

-   -   R₈ to R₁₁, which may be identical or different, represent a        linear or branched aliphatic group comprising from 1 to 30        carbon atoms, or an aromatic group such as aryl or alkylaryl, it        being understood that at least one of the groups R₈ to R₁₁        comprises from 8 to 30 carbon atoms and preferably from 12 to 24        carbon atoms; and    -   X⁻ represents an organic or inorganic anionic counterion, such        as that chosen from halides, acetates, phosphates, nitrates,        (C₁-C₄)alkyl sulfates, (C₁-C₄)alkyl or (C₁-C₄)alkylaryl        sulfonates, in particular methyl sulfate and ethyl sulfate.        The aliphatic groups of R₈ to R₁₁ may also comprise heteroatoms        especially such as oxygen, nitrogen, sulfur and halogens.

The aliphatic groups of R₈ to R₁₁ are chosen, for example, from C₁-C₃₀alkyl, C₁-C₃₀ alkoxy, polyoxy(C₂-C₆)alkylene, C₁-C₃₀ alkylamide,(C₁₂-C₂₂)alkylamido(C₂-C₆)alkyl, (C₁₂-C₂₂)alkyl acetate and C₁-C₃₀hydroxyalkyl groups, X⁻ is an anionic counterion chosen from the groupof halides, phosphates, acetates, lactates, (C₁-C₄)alkyl sulfates and(C₁-C₄)alkyl- or (C₁-C₄)alkylarylsulfonates.

Among the quaternary ammonium salts of formula (B3), preference is givenfirstly to tetraalkylammonium chlorides, for instancedialkyldimethylammonium or alkyltrimethylammonium chlorides in which thealkyl group comprises approximately from 12 to 22 carbon atoms, inparticular behenyltrimethylammonium chloride, distearyldimethylammoniumchloride, cetyltrimethylammonium chloride, benzyldimethylstearylammoniumchloride, or else, secondly, distearoylethylhydroxyethylmethylammoniummethosulfate, dipalmitoylethylhydroxyethylammonium methosulfate ordistearoylethylhydroxyethylammonium methosulfate, or else, lastly,palmitylamidopropyltrimethylammonium chloride orstearamidopropyldimethyl(myristyl acetate)ammonium chloride, sold underthe name Ceraphyl® 70 by the company Van Dyk;

-   quaternary ammonium salts of imidazoline, for instance those of    formula (B4) below:

in which formula:

-   -   R₁₂ represents an alkenyl or alkyl group comprising from 8 to 30        carbon atoms, for example fatty acid derivatives of tallow;    -   R₁₃ represents a hydrogen atom, a C₁-C₄ alkyl group or an        alkenyl or alkyl group comprising from 8 to 30 carbon atoms;    -   R₁₄ represents a C₁-C₄ alkyl group;    -   R₁₅ represents a hydrogen atom or a C₁-C₄ alkyl group;    -   X⁻ represents an organic or inorganic anionic counterion, such        as that chosen from halides, phosphates, acetates, lactates,        (C₁-C₄)alkyl sulfates, (C₁-C₄)alkyl or (C₁-C₄)alkylaryl        sulfonates.

R₁₂ and R₁₃ preferably denote a mixture of alkyl or alkenyl groupscontaining from 12 to 21 carbon atoms, for example tallow fatty acidderivatives, R₁₄ denotes a methyl group, and R₁₅ denotes a hydrogenatom. Such a product is sold, for example, under the name Rewoquat® W 75by the company Rewo;

-   quaternary diammonium or triammonium salts, in particular of formula    (B5) below:

in which formula:

-   -   R₁₆ denotes an alkyl group comprising approximately from 16 to        30 carbon atoms, which is optionally hydroxylated and/or        interrupted with one or more oxygen atoms;    -   R₁₇ is chosen from hydrogen, an alkyl group comprising from 1 to        4 carbon atoms or a group —(CH₂)₃—N⁺(R_(16a))(R_(17a))(R_(18a)),        X⁻;    -   R_(16a), R_(17a), R_(18a), R₁₈, R₁₉, R₂₀ and R₂₁, which may be        identical or different, are chosen from hydrogen and an alkyl        group comprising from 1 to 4 carbon atoms; and    -   X⁻, which may be identical or different, represent an organic or        inorganic anionic counterion, such as that chosen from halides,        acetates, phosphates, nitrates, (C₁-C₄)alkyl sulfates,        (C₁-C₄)alkyl or (C₁-C₄)alkylaryl sulfonates, in particular        methyl sulfate and ethyl sulfate.

Such compounds are, for example, Finquat CT-P, sold by the companyFinetex (Quaternium 89), and Finquat CT, sold by the company Finetex(Quaternium 75);

-   quaternary ammonium salts containing one or more ester functions,    such as those of formula (B6) below:

in which formula:

-   -   R₂₂ is chosen from C₁-C₆ alkyl groups and C₁-C₆ hydroxyalkyl or        C₁-C₆ dihydroxyalkyl groups,    -   R₂₃ is chosen from:        -   the group

-   -   -   linear or branched, saturated or unsaturated C₁-C₂₂            hydrocarbon-based groups R₂₇,        -   a hydrogen atom,

    -   R₂₅ is chosen from:        -   the group

-   -   -   linear or branched, saturated or unsaturated C₁-C₆            hydrocarbon-based groups R₂₉,        -   a hydrogen atom,

    -   R₂₄, R₂₆ and R₂₈, which are identical or different, are chosen        from linear or branched, saturated or unsaturated C₇-C₂₁        hydrocarbon groups;

    -   r, s and t, which may be identical or different, are integers        ranging from 2 to 6,

    -   r1 and t1, which may be identical or different, are equal to 0        or 1, with r2+r1=2r and t1+t2=2t,

    -   y is an integer ranging from 1 to 10,

    -   x and z, which may be identical or different, are integers        ranging from 0 to 10,

    -   X⁻ represents an organic or inorganic anionic counterion, with        the proviso that the sum x+y+z equals from 1 to 15, that, when x        is 0, then R₂₃ denotes R₂₇ and that, when z is 0, then R₂₅        denotes R₂₉.

The alkyl groups R₂₂ may be linear or branched, and more particularlylinear.

Preferably, R₂₂ denotes a methyl, ethyl, hydroxyethyl or dihydroxypropylgroup, and more particularly a methyl or ethyl group.

Advantageously, the sum x+y+z is from 1 to 10.

When R₂₃ is an R₂₇ hydrocarbon-based group, it may be long and maycontain from 12 to 22 carbon atoms, or may be short and may contain from1 to 3 carbon atoms.

When R₂₅ is an R₂₉ hydrocarbon-based group, it preferably contains 1 to3 carbon atoms.

Advantageously, R₂₄, R₂₆ and R₂₈, which are identical or different, areselected from linear or branched, saturated or unsaturated C₁₁-C₂₁hydrocarbon-based groups, and more particularly from linear or branched,saturated or unsaturated C₁₁-C₂₁ alkyl and alkenyl groups.

Preferably, x and z, which may be identical or different, are equal to 0or 1.

y is advantageously equal to 1.

Preferably, r, s and t, which may be identical or different, equal 2 or3, and even more particularly are equal to 2.

The anionic counterion X⁻ is preferably a halide, such as chloride,bromide or iodide; a (C₁-C₄)alkyl sulfate or a (C₁-C₄)alkyl- or(C₁-C₄)alkylarylsulfonate. However, it is possible to usemethanesulfonate, phosphate, nitrate, tosylate, an anion derived from anorganic acid, such as acetate or lactate, or any other anion that iscompatible with the ammonium containing an ester function.

The anionic counterion X⁻ is even more particularly chloride, methylsulfate or ethyl sulfate.

Use is made more particularly in the dye composition according to theinvention of the ammonium salts of formula (B6) in which:

-   -   R₂₂ denotes a methyl or ethyl group,    -   x and y are equal to 1,    -   z is equal to 0 or 1,    -   r, s and t are equal to 2,    -   R₂₃ is chosen from:        -   the group

-   -   -   methyl, ethyl or C₁₄-C₂₂ hydrocarbon-based groups,        -   a hydrogen atom,

    -   R₂₅ is chosen from:        -   the group

-   -   -   a hydrogen atom,

    -   R₂₄, R₂₆ and R₂₈, which may be identical or different, are        chosen from linear or branched, saturated or unsaturated C₁₃-C₁₇        hydrocarbon-based groups, and preferably from linear or        branched, saturated or unsaturated C₁₃-C₁₇ alkyl and alkenyl        groups.

Advantageously, the hydrocarbon-based radicals are linear.

Among the compounds of formula (B6), examples that may be mentionedinclude salts, especially the chloride or methyl sulfate, ofdiacyloxyethyldimethylammonium,diacyloxyethylhydroxyethylmethylammonium,monoacyloxyethyldihydroxyethylmethylammonium,triacyloxyethylmethylammonium ormonoacyloxyethylhydroxyethyldimethylammonium, and mixtures thereof. Theacyl groups preferably contain 14 to 18 carbon atoms and originate moreparticularly from a plant oil such as palm oil or sunflower oil. Whenthe compound contains several acyl groups, these groups may be identicalor different.

These products are obtained, for example, by direct esterification oftriethanolamine, triisopropanolamine, an alkyldiethanolamine or analkyldiisopropanolamine, which are optionally oxyalkylenated, with fattyacids or with fatty acid mixtures of plant or animal origin, or bytransesterification of the methyl esters thereof. This esterification isfollowed by a quaternization by means of an alkylating agent such as analkyl halide, preferably methyl or ethyl halide, a dialkyl sulfate,preferably dimethyl or diethyl sulfate, methyl methanesulfonate, methylpara-toluenesulfonate, glycol chlorohydrin or glycerol chlorohydrin.

Such compounds are sold, for example, under the names Dehyquart® by thecompany Henkel, Stepanquat® by the company Stepan, Noxamium® by thecompany Ceca or Rewoquat® WE 18 by the company Rewo-Witco.

The dye composition may contain, for example, a mixture of quaternaryammonium monoester, diester and triester salts with a weight majority ofdiester salts.

It is also possible to use the ammonium salts containing at least oneester function that are described in U.S. Pat. No. 4,874,554 and U.S.Pat. No. 4,137,180.

Use may be made of behenoylhydroxypropyltrimethylammonium chloride soldby KAO under the name Quatarmin BTC 131.

Preferably, the ammonium salts containing at least one ester functioncontain two ester functions.

Among the cationic surfactants that may be present in the dyecomposition, it is more particularly preferred to choosecetyltrimethylammonium, behenyltrimethylammonium anddipalmitoylethylhydroxyethylmethylammonium salts, and mixtures thereof,and more particularly behenyltrimethylammonium chloride,cetyltrimethylammonium chloride, anddipalmitoylethylhydroxyethylammonium methosulfate, and mixtures thereof.

Examples of nonionic surfactants that may be used in the compositionused according to the invention are described, for example, in theHandbook of Surfactants by M. R. Porter, published by Blackie & Son(Glasgow and London), 1991, pp. 116-178. They are especially chosen fromalcohols, α-diols and (C₁-C₂₀)alkylphenols, these compounds beingetherified with ethoxylated and/or propoxylated groups, and containingat least one fatty chain comprising, for example, from 8 to 18 carbonatoms, it being possible for the number of ethylene oxide and/orpropylene oxide groups to range especially from 1 to 100, moreparticularly from 2 to 50 and even more particularly from 2 to 30.

Mention may also be made of copolymers of ethylene oxide and propyleneoxide, optionally oxyethylenated fatty acid esters of sorbitan, fattyacid esters of sucrose, polyoxyalkylenated fatty acid esters, optionallyoxyalkylenated alkyl polyglycosides, alkyl glucoside esters, derivativesof N-alkyl glucamine and of N-acyl methylglucamine, aldobionamides andamine oxides.

The nonionic surfactants are more particularly chosen fromoxyalkylenated nonionic surfactants. The oxyalkylene units are moreparticularly oxyethylene or oxypropylene units, or a combinationthereof, preferably oxyethylene units.

Examples of oxyalkylenated nonionic surfactants that may be mentionedinclude:

-   -   oxyalkylenated (C₈-C₂₄)alkylphenols;    -   saturated or unsaturated, linear or branched, oxyalkylenated        C₈-C₃₀ alcohols;    -   saturated or unsaturated, linear or branched, oxyalkylenated        C₈-C₃₀ amides;    -   esters of saturated or unsaturated, linear or branched, C₈-C₃₀        acids and of polyethylene glycols;    -   oxyethylenated esters of saturated or unsaturated, linear or        branched C₈-C₃₀ acids and of sorbitol;    -   saturated or unsaturated oxyethylenated vegetable oils;    -   condensates of ethylene oxide and/or of propylene oxide, inter        alia, alone or as mixtures;    -   oxyethylenated and/or oxypropylenated silicones.

The surfactants contain a number of moles of ethylene oxide and/or ofpropylene oxide of between 1 and 100, preferably between 2 and 50 andeven more preferentially between 2 and 30. Advantageously, the nonionicsurfactants do not comprise any oxypropylene units.

In accordance with a preferred embodiment of the invention, theoxyalkylenated nonionic surfactants are chosen from oxyethylenatedC₈-C₃₀ alcohols comprising from 1 to 100 mol of ethylene oxide,preferably between 2 and 50 and even more preferentially between 2 and30 mol of ethylene oxide; oxyethylenated esters of linear or branched,saturated or unsaturated C₈-C₃₀ acids and of sorbitol comprising from 1to 100 mol of ethylene oxide.

Preferably, the additional surfactant(s) are chosen from nonionic,anionic and amphoteric surfactants. More particularly, the additionalsurfactant(s) present in the composition are chosen from nonionicsurfactants.

Preferably, the additional surfactant(s), when they are present, arechosen from oxyalkylenated, particularly oxyethylenated oroxypropylenated, nonionic surfactants, or a combination thereof, moreparticularly oxyethylenated.

Even more preferentially, the nonionic surfactants are chosen fromoxyethylenated sorbitol esters, oxyethylenated fatty alcohols, andmixtures thereof.

In the dye composition, the amount of additional surfactant(s), whenthey are present, preferably ranges from 0.1% to 50% by weight andbetter still from 0.5% to 20% by weight relative to the total weight ofthe said composition.

Medium

The medium of the dye composition according to the invention isadvantageously an aqueous medium. It may also comprise one or moreorganic solvents.

Examples of organic solvents that may be mentioned include linear orbranched and preferably saturated monoalcohols or diols, comprising 2 to10 carbon atoms, such as ethyl alcohol, isopropyl alcohol, hexyleneglycol (2-methyl-2,4-pentanediol), neopentyl glycol and3-methyl-1,5-pentanediol, butylene glycol, dipropylene glycol andpropylene glycol; aromatic alcohols such as benzyl alcohol orphenylethyl alcohol; polyols containing more than two hydroxylfunctions, such as glycerol; polyol ethers, for instance ethylene glycolmonomethyl, monoethyl or monobutyl ether, propylene glycol or ethersthereof, for instance propylene glycol monomethyl ether; and alsodiethylene glycol alkyl ethers, especially C₁-C₄ alkyl ethers, forinstance diethylene glycol monoethyl ether or monobutyl ether, alone oras a mixture.

The organic solvents, when they are present, generally represent between1% and 40% by weight relative to the total weight of the dyecomposition, and preferably between 5% and 30% by weight relative to thetotal weight of the dye composition.

The dye composition is preferably aqueous. In this case, it preferablycomprises from 30% to 95% by weight of water, better still from 40% to90% by weight of water and even better still from 50% to 85% by weightof water relative to the total weight of the composition.

The pH of the dye composition, if it is aqueous, is generally between 3and 12 and preferably between 5 and 11. Preferentially between 7 and 11,limits included.

It may be adjusted to the desired value by means of acidifying orbasifying agents usually used in the dyeing of keratin fibres, and inparticular the alkaline agents of the invention mentioned above.

Fatty Substances

The dye composition may optionally comprise one or more fattysubstances.

The term “fatty substance” means an organic compound that is insolublein water at ordinary temperature (25° C.) and at atmospheric pressure(760 mmHg) (solubility of less than 5%, preferably less than 1% and evenmore preferentially less than 0.1%). They exhibit, in their structure,at least one hydrocarbon chain comprising at least 6 carbon atoms or asequence of at least two siloxane groups. In addition, the fattysubstances are generally soluble in organic solvents under the sametemperature and pressure conditions, for instance chloroform,dichloromethane, carbon tetrachloride, ethanol, benzene, toluene,tetrahydrofuran (THF), liquid petroleum jelly ordecamethylcyclopentasiloxane.

The fatty substances of the invention do not contain any salified orunsalified carboxylic acid groups (COOH or COO—).

Particularly, the fatty substances of the invention are neither(poly)oxyalkylenated nor (poly)glycerolated.

The term “oil” means a “fatty substance” that is liquid at roomtemperature (25° C.) and at atmospheric pressure (760 mmHg).

The term “non-silicone oil” means an oil not containing any siliconatoms (Si) and the term “silicone oil” means an oil containing at leastone silicon atom.

More particularly, the fatty substances are chosen from C₆-C₁₆hydrocarbons, hydrocarbons containing more than 16 carbon atoms,non-silicone oils of animal origin, plant oils of triglyceride type,synthetic triglycerides, fluoro oils, fatty alcohols, fatty acid and/orfatty alcohol esters other than triglycerides and plant waxes,non-silicone waxes and silicones, and mixtures thereof.

It is recalled that the fatty alcohols, esters and acids moreparticularly have at least one linear or branched, saturated orunsaturated hydrocarbon-based group comprising 6 to 30 and better stillfrom 8 to 30 carbon atoms, which is optionally substituted, inparticular with one or more hydroxyl groups (in particular 1 to 4). Ifthey are unsaturated, these compounds may comprise one to threeconjugated or unconjugated carbon-carbon double bonds.

As regards the C₆-C₁₆ hydrocarbons, they are linear, branched oroptionally cyclic, and are preferably alkanes. Examples that may bementioned include hexane, dodecane and isoparaffins such asisohexadecane and isodecane.

A hydrocarbon-based oil of animal origin that may be mentioned isperhydrosqualene.

The triglyceride oils of plant or synthetic origin are preferably chosenfrom liquid fatty acid triglycerides containing from 6 to 30 carbonatoms, for instance heptanoic or octanoic acid triglycerides, oralternatively, for example, sunflower oil, corn oil, soybean oil, marrowoil, grapeseed oil, sesame seed oil, hazelnut oil, apricot oil,macadamia oil, arara oil, castor oil, avocado oil, caprylic/capric acidtriglycerides, for instance those sold by the company StéarineriesDubois or those sold under the names Miglyol® 810, 812 and 818 by thecompany Dynamit Nobel, jojoba oil and shea butter oil.

The linear or branched hydrocarbons of mineral or synthetic originhaving more than 16 carbon atoms are preferably chosen from liquidparaffins, petroleum jelly, liquid petroleum jelly, polydecenes orhydrogenated polyisobutene, such as Parleam®.

As regards the C₆-C₁₆ alkanes, they are linear or branched, and possiblycyclic. Examples that may be mentioned include hexane, dodecane andisoparaffins such as isohexadecane and isodecane.

As oils of animal, vegetable, mineral or synthetic origin that may beused in the composition of the invention, examples that may be mentionedinclude:

the fluoro oils that may be chosen from perfluoromethylcyclopentane andperfluoro-1,3-dimethylcyclohexane, sold under the names Flutec® PC1 andFlutec® PC3 by the company BNFL Fluorochemicals;perfluoro-1,2-dimethylcyclobutane; perfluoroalkanes such asdodecafluoropentane and tetradecafluorohexane, sold under the names PF5050® and PF 5060® by the company 3M, or bromoperfluorooctyl sold underthe name Foralkyl® by the company Atochem; nonafluoromethoxybutane andnonafluoroethoxyisobutane; perfluoromorpholine derivatives such as4-trifluoromethyl perfluoromorpholine sold under the name PF 5052® bythe company 3M.

The fatty alcohols which are suitable for the implementation of theinvention are more particularly chosen from saturated or unsaturated,linear or branched alcohols comprising from 6 to 30 carbon atoms andpreferably from 8 to 30 carbon atoms. Mention may be made, for example,of cetyl alcohol, stearyl alcohol and the mixture thereof (cetearylalcohol), octyldodecanol, 2-butyloctanol, 2-hexyldecanol,2-undecylpentadecanol, oleyl alcohol or linoleyl alcohol.

As regards the esters of a fatty acid and/or of fatty alcohols, whichare advantageously different from the triglycerides mentionedpreviously, mention may be made especially of esters of saturated orunsaturated, linear or branched C₁-C₂₆ aliphatic monoacids or polyacidsand of saturated or unsaturated, linear or branched C₁-C₂₆ aliphaticmonoalcohols or polyalcohols, the total carbon number of the estersbeing greater than or equal to 6 and more advantageously greater than orequal to 10.

Among the monoesters, mention may be made of dihydroabietyl behenate;octyldodecyl behenate; isocetyl behenate; cetyl lactate; C₁₂-C₁₅ alkyllactate; isostearyl lactate; lauryl lactate; linoleyl lactate; oleyllactate; (iso)stearyl octanoate; isocetyl octanoate; octyl octanoate;cetyl octanoate; decyl oleate; isocetyl isostearate; isocetyl laurate;isocetyl stearate; isodecyl octanoate; isodecyl oleate; isononylisononanoate; isostearyl palmitate; methylacetyl ricinoleate; myristylstearate; octyl isononanoate; 2-ethylhexyl isononanoate; octylpalmitate; octyl pelargonate; octyl stearate; octyldodecyl erucate;oleyl erucate; ethyl and isopropyl palmitates, 2-ethylhexyl palmitate,2-octyldecyl palmitate, alkyl myristates such as isopropyl, butyl,cetyl, 2-octyldodecyl, myristyl or stearyl myristate, hexyl stearate,butyl stearate, isobutyl stearate; dioctyl malate, hexyl laurate,2-hexyldecyl laurate.

Still within the context of this variant, esters of C₄-C₂₂ dicarboxylicor tricarboxylic acids and of C₁-C₂₂ alcohols and esters of mono-, di-or tricarboxylic acids and of C₂-C₂₆ di-, tri-, tetra- or pentahydroxyalcohols may also be used.

Mention may be made especially of: diethyl sebacate; diisopropylsebacate; diisopropyl adipate; di-n-propyl adipate; dioctyl adipate;diisostearyl adipate; dioctyl maleate; glyceryl undecylenate;octyldodecyl stearoyl stearate; pentaerythrityl monoricinoleate;pentaerythrityl tetraisononanoate; pentaerythrityl tetrapelargonate;pentaerythrityl tetraisostearate; pentaerythrityl tetraoctanoate;propylene glycol dicaprylate; propylene glycol dicaprate; tridecylerucate; triisopropyl citrate; triisostearyl citrate; glyceryltrilactate; glyceryl trioctanoate; trioctyldodecyl citrate; trioleylcitrate; propylene glycol dioctanoate; neopentyl glycol diheptanoate;diethylene glycol diisononanoate; and polyethylene glycol distearates.

Among the esters mentioned above, it is preferred to use ethyl,isopropyl, myristyl, cetyl or stearyl palmitate, 2-ethylhexyl palmitate,2-octyldecyl palmitate, alkyl myristates such as isopropyl, butyl, cetylor 2-octyldodecyl myristate, hexyl stearate, butyl stearate, isobutylstearate; dioctyl malate, hexyl laurate, 2-hexyldecyl laurate, isononylisononanoate or cetyl octanoate.

The composition may also comprise, as fatty ester, sugar esters anddiesters of C₆-C₃₀ and preferably C₁₂-C₂₂ fatty acids. It is recalledthat the term “sugar” means oxygen-bearing hydrocarbon-based compoundswhich have several alcohol functions, with or without aldehyde or ketonefunctions, and which comprise at least 4 carbon atoms. These sugars canbe monosaccharides, oligosaccharides or polysaccharides.

Mention may be made, as suitable sugars, for example, of sucrose (orsaccharose), glucose, galactose, ribose, fucose, maltose, fructose,mannose, arabinose, xylose and lactose, and derivatives thereof, inparticular alkyl derivatives, such as methyl derivatives, for instancemethylglucose.

The sugar esters of fatty acids may be chosen in particular from thegroup comprising the esters or mixtures of esters of sugars describedpreviously and of linear or branched, saturated or unsaturated C₆-C₃₀and preferably C₁₂-C₂₂ fatty acids. If they are unsaturated, thesecompounds may comprise one to three conjugated or unconjugatedcarbon-carbon double bonds.

The esters according to this variant may also be chosen from mono-, di-,tri- and tetraesters, polyesters, and mixtures thereof.

These esters can, for example, be oleates, laurates, palmitates,myristates, behenates, cocoates, stearates, linoleates, linolenates,caprates, arachidonates or mixtures thereof, such as, in particular,oleate/palmitate, oleate/stearate or palmitate/stearate mixed esters.

More particularly, use is made of monoesters and diesters and inparticular mono- or di-oleate, -stearate, -behenate, -oleate/palmitate,-linoleate, -linolenate or -oleate/stearate of sucrose, of glucose or ofmethylglucose.

An example that may be mentioned is the product sold under the nameGlucate® DO by the company Amerchol, which is a methylglucose dioleate.

Examples of esters or mixtures of esters of sugar and of fatty acid thatmay also be mentioned include:

-   -   the products sold under the names F160, F140, F110, F90, F70 and        SL40 by the company Crodesta, respectively denoting sucrose        palmitostearates formed from 73% monoester and 27% diester and        triester, from 61% monoester and 39% diester, triester and        tetraester, from 52% monoester and 48% diester, triester and        tetraester, from 45% monoester and 55% diester, triester and        tetraester, from 39% monoester and 61% diester, triester and        tetraester, and sucrose monolaurate;    -   the products sold under the name Ryoto Sugar Esters, for        example, referenced B370 and corresponding to sucrose behenate        formed from 20% monoester and 80% diester-triester-polyester;    -   the sucrose mono-di-palmito-stearate sold by the company        Goldschmidt under the name Tegosoft® PSE.

The non-silicone wax(es) are chosen in particular from carnauba wax,candelilla wax, esparto wax, paraffin wax, ozokerite, vegetable waxes,such as olive tree wax, rice wax, hydrogenated jojoba wax or absoluteflower waxes, such as the blackcurrant blossom essential wax sold byBertin (France), or animal waxes, such as beeswaxes or modifiedbeeswaxes (cerabellina); other waxes or waxy starting materials whichcan be used according to the invention are in particular marine waxes,such as that sold by Sophim under the reference M82, polyethylene waxesor polyolefin waxes in general.

The silicones that may be used in the dye composition of the presentinvention are volatile or non-volatile, cyclic, linear or branchedsilicones, which are unmodified or modified with organic groups, havinga viscosity from 5×10⁻⁶ to 2.5 m²/s at 25° C., and preferably 1×10⁻⁵ to1 m²/s.

The silicones that may be used in accordance with the invention may bein the form of oils, waxes, resins or gums.

Preferably, the silicone is chosen from polydialkylsiloxanes, especiallypolydimethylsiloxanes (PDMS), and organomodified polysiloxanescomprising at least one functional group chosen from amino groups andalkoxy groups.

Organopolysiloxanes are defined in greater detail in Walter Noll'sChemistry and Technology of Silicones (1968), Academic Press. They maybe volatile or non-volatile.

When they are volatile, the silicones are more particularly chosen fromthose having a boiling point of between 60° C. and 260° C., and moreparticularly still from:

(i) cyclic polydialkylsiloxanes containing from 3 to 7 and preferablyfrom 4 to 5 silicon atoms. These are, for example,octamethylcyclotetrasiloxane sold in particular under the name VolatileSilicone® 7207 by Union Carbide or Silbione® 70045 V2 by Rhodia,decamethylcyclopentasiloxane sold under the name Volatile Silicone® 7158by Union Carbide, and Silbione® 70045 V5 by Rhodia, and mixturesthereof.

Mention may also be made of cyclocopolymers of thedimethylsiloxane/methylalkylsiloxane type, such as Volatile Silicone® FZ3109 sold by the company Union Carbide, of formula:

Mention may also be made of mixtures of cyclic polydialkylsiloxanes withorganosilicon compounds, such as the mixture ofoctamethylcyclotetrasiloxane and tetra(trimethylsilyl)pentaerythritol(50/50) and the mixture of octamethylcyclotetrasiloxane andoxy-1,1′-bis(2,2,2′,2′,3,3′-hexatrimethylsilyloxy)neopentane;

(ii) linear volatile polydialkylsiloxanes containing 2 to 9 siliconatoms and having a viscosity of less than or equal to 5×10⁻⁶ m²/s at 25°C. An example is decamethyltetrasiloxane sold in particular under thename SH 200 by the company Toray Silicone. Silicones belonging to thiscategory are also described in the article published in Cosmetics andToiletries, Vol. 91, January 76, pp. 27-32, Todd & Byers, VolatileSilicone Fluids for Cosmetics.

Use is preferably made of non-volatile polydialkylsiloxanes,polydialkylsiloxane gums and resins, polyorganosiloxanes modified withthe organofunctional groups above, and mixtures thereof.

These silicones are more particularly chosen from polydialkylsiloxanes,among which mention may be made mainly of polydimethylsiloxanes havingtrimethylsilyl end groups. The viscosity of the silicones is measured at25° C. according to ASTM standard 445 Appendix C.

Mention may be made, among these polydialkylsiloxanes, without impliedlimitation, of the following commercial products:

-   the Silbione® oils of the 47 and 70 047 series or the Mirasil® oils    sold by Rhodia, such as, for example, the oil 70 047 V 500 000;-   the oils of the Mirasil® series sold by Rhodia;-   the oils of the 200 series from the company Dow Corning, such as    DC200 with a viscosity of 60 000 mm²/s;-   the Viscasil® oils from General Electric and certain oils of the SF    series (SF 96, SF 18) from General Electric.

Mention may also be made of polydimethylsiloxanes bearingdimethylsilanol end groups known under the name dimethiconol (CTFA),such as the oils of series 48 from the company Rhodia.

In this category of polydialkylsiloxanes, mention may also be made ofthe products sold under the names Abil Wax® 9800 and 9801 by the companyGoldschmidt, which are polydi(C₁-C₂₀)alkylsiloxanes.

The silicone gums that may be used in accordance with the invention arein particular polydialkylsiloxanes and preferably polydimethylsiloxaneswith high number-average molecular weights of between 200 000 and 1 000000, used alone or as a mixture in a solvent. This solvent can be chosenfrom volatile silicones, polydimethylsiloxane (PDMS) oils,polyphenylmethylsiloxane (PPMS) oils, isoparaffins, polyisobutylenes,methylene chloride, pentane, dodecane, tridecane or their mixtures.

Products which can be used more particularly in accordance with theinvention are mixtures such as:

-   -   the mixtures formed from a polydimethylsiloxane hydroxylated at        the chain end, or dimethiconol (CTFA), and from a cyclic        polydimethylsiloxane, also known as cyclomethicone (CTFA), such        as the product Q2 1401 sold by Dow Corning;    -   the mixtures of a polydimethylsiloxane gum and of a cyclic        silicone, such as the product SF 1214 Silicone Fluid from        General Electric; this product is an SF 30 gum corresponding to        a dimethicone, having a number-average molecular weight of 500        000, dissolved in the oil SF 1202 Silicone Fluid corresponding        to decamethylcyclopentasiloxane;    -   the mixtures of two PDMSs with different viscosities, and more        particularly of a PDMS gum and a PDMS oil, such as the product        SF 1236 from General Electric. The product SF 1236 is a mixture        of a gum SE 30 defined above, with a viscosity of 20 m²/s, and        of an oil SF 96 with a viscosity of 5×10⁻⁶ m²/s. This product        preferably comprises 15% of gum SE 30 and 85% of an oil SF 96.

The organopolysiloxane resins that may be used in accordance with theinvention are crosslinked siloxane systems containing the followingunits:

R₂SiC_(2/2), R₃SiCO_(1/2), RSiO_(3/2) and SiO_(4/2),

in which R represents an alkyl containing 1 to 16 carbon atoms. Amongthese products, those that are particularly preferred are those in whichR denotes a C₁-C₄ lower alkyl group, more particularly methyl.

Mention may be made, among these resins, of the product sold under thename Dow Corning 593 or those sold under the names Silicone Fluid SS4230 and SS 4267 by General Electric, which are silicones ofdimethyl/trimethylsiloxane structure.

Mention may also be made of the resins of the trimethylsiloxysilicatetype, sold especially under the names X22-4914, X21-5034 and X21-5037 bythe company Shin-Etsu.

The organomodified silicones that may be used in accordance with theinvention are silicones as defined above and comprising in theirstructure one or more organofunctional groups attached via ahydrocarbon-based group.

In addition to the silicones described above, the organomodifiedsilicones can be polydiarylsiloxanes, in particularpolydiphenylsiloxanes, and polyalkylarylsiloxanes functionalized by theabovementioned organofunctional groups.

The polyalkylarylsiloxanes are chosen particularly from linear and/orbranched polydimethyl/methylphenylsiloxanes andpolydimethyl/diphenylsiloxanes with a viscosity of from 1×10⁻⁵ to 5×10⁻²m²/s at 25° C.

Among these polyalkylarylsiloxanes, examples that may be mentionedinclude the products sold under the following names:

-   -   the Silbione® oils of the 70 641 series from Rhodia;    -   the oils of the Rhodorsil® 70 633 and 763 series from Rhodia;    -   the oil Dow Corning 556 Cosmetic Grade Fluid from Dow Corning;    -   the silicones of the PK series from Bayer, such as the product        PK20;    -   the silicones of the PN and PH series from Bayer, such as the        products PN1000 and PH1000;    -   certain oils of the SF series from General Electric, such as SF        1023, SF 1154, SF 1250 and SF 1265.

Mention may be made, among the organomodified silicones, ofpolyorganosiloxanes comprising:

-   -   substituted or unsubstituted amine groups, such as the products        sold under the name GP 4 Silicone Fluid and GP 7100 by the        company Genesee, or the products sold under the names Q2 8220        and Dow Corning 929 or 939 by the company Dow Corning. The        substituted amine groups are, in particular, C₁-C₄ aminoalkyl        groups;    -   alkoxylated groups, such as the product sold under the name        Silicone Copolymer F-755 by SWS Silicones, and Abil Wax® 2428,        2434 and 2440 by the company Goldschmidt.

More particularly, the fatty substances are chosen from compounds thatare liquid or pasty at room temperature (25° C.) and at atmosphericpressure.

Preferably, the fatty substance is a compound that is liquid at atemperature of 25° C. and at atmospheric pressure.

The fatty substances are advantageously chosen from C₆-C₁₆ alkanes,non-silicone oils of plant, mineral or synthetic origin, fatty alcohols,and esters of a fatty acid and/or of a fatty alcohol, or mixturesthereof.

Preferably, the fatty substance is chosen from liquid petroleum jelly,C₆-C₁₆ alkanes, polydecenes, liquid esters of a fatty acid and/or of afatty alcohol, and liquid fatty alcohols, or mixtures thereof.

In a first variant of the invention, the total content of fattysubstances in the mixture, when they are present, is less than 20% byweight relative to the total weight of the composition (mixture of thedye and oxidizing compositions). It then preferably ranges from acontent of more than 0 to 19%, better still from a content of more than0 to 15% and even better still from a content of more than 0 to 10% byweight relative to the total weight of the composition (mixture of thedye and oxidizing compositions).

In a second variant of the invention, the total content of fattysubstances is greater than or equal to 20% by weight relative to thetotal weight of the composition. It then preferably ranges from 20% to80%, better still from 30% to 75% and even better still from 50% to 70%by weight relative to the total weight of the composition (mixture ofthe dye and oxidizing compositions).

Other Adjuvants

The dye composition may also contain various adjuvants which areconventionally used in hair dye compositions, for instance anionic,cationic, nonionic, amphoteric or zwitterionic polymers or mixturesthereof; thickeners such as crosslinked acrylic acid homopolymers,cellulose-based thickeners (with, for example, hydroxyethylcellulose,hydroxypropylcellulose or carboxymethylcellulose), guar gum andderivatives thereof (for example hydroxypropylguar), gums of microbialorigin (especially xanthan gum or scleroglucan gum); mineral thickenersespecially such as clays; ammonium salts such as ammonium chloride orammonium acetate; antioxidants or reducing agents such as ascorbic acid,erythorbic acid, ammonium sulfite, bisulfite or metabisulfite, orammonium thiolactate; penetrants, sequestrants such asethylenediaminetetraacetic or salts thereof; fragrances; titaniumoxides; buffers; dispersants; and preserving agents, or mixturesthereof.

The above adjuvants are generally present in an amount for each of themof between 0.01% and 20% by weight relative to the weight of thecomposition.

Oxidizing Composition

Chemical Oxidizing Agent

The second composition used in the process according to the inventionalso comprises at least one chemical oxidizing agent.

It should be noted that the oxidizing agents present in the oxidizingcomposition are termed “chemical” to distinguish them from atmosphericoxygen.

In particular, the chemical oxidizing agent(s) that are suitable for usein the present invention are chosen, for example, from hydrogenperoxide, urea peroxide, alkali metal bromates or ferricyanides,peroxygenated salts, for instance persulfates, perborates, peracids andprecursors thereof and percarbonates of alkali metals or alkaline-earthmetals. Advantageously, the oxidizing agent is hydrogen peroxide.

The content of oxidizing agent(s) more particularly represents from 0.1%to 20% by weight and preferably from 0.5% to 10% by weight relative tothe weight of the oxidizing composition.

Additional Surfactants

The oxidizing composition may also comprise one or more additionalsurfactants which are chosen from additional surfactants other than theabovementioned glycerolated fatty alcohol surfactant(s) and other thanthe oxyalkylenated carboxylic acid ether in acid or salified form.

In particular, the additional surfactant(s) are chosen from anionicsurfactants other than the oxyalkylenated carboxylic acid ether in acidor salified form, amphoteric, zwitterionic, cationic and nonionicsurfactants other than the said glycerolated fatty alcohols, andpreferentially nonionic surfactants. Reference may be made to the listof compounds of this type given in the context of the description of thedye composition.

Preferably, these surfactants, if they are present, are chosen fromnonionic surfactants.

Even more preferably, the oxyalkylenated nonionic surfactants are chosenfrom oxyethylenated C₈-C₃₀ alcohols comprising from 1 to 100 mol ofethylene oxide, preferably from 2 to 50 and better still from 2 to 30mol of ethylene oxide; oxyalkylenated, linear or branched, saturated orunsaturated C₈-C₃₀ amides comprising from 1 to 100 mol of ethyleneoxide, preferably from 2 to 50 and better still from 2 to 30 mol ofethylene oxide; oxyethylenated esters of linear or branched, saturatedor unsaturated C₈-C₃₀ acids and of sorbitol comprising from 1 to 100 molof ethylene oxide.

In the oxidizing composition, the amount of additional surfactant(s),when they are present, preferably ranges from 0.1% to 50% by weight andbetter still from 0.5% to 20% by weight relative to the total weight ofthe said composition.

Medium

The oxidizing composition is advantageously an aqueous composition. Itmay also comprise one or more organic solvents chosen from those listedpreviously, these solvents more particularly representing, when they arepresent, from 1% to 40% by weight and preferably from 5% to 30% byweight relative to the weight of the oxidizing composition.

The oxidizing composition also preferably comprises one or moreacidifying agents. Among the acidifying agents, examples that may bementioned include mineral or organic acids, for instance hydrochloricacid, orthophosphoric acid, sulfuric acid, carboxylic acids, forinstance acetic acid, tartaric acid, citric acid or lactic acid, andsulfonic acids.

Usually, the pH of the oxidizing composition, when it is aqueous, isless than 7.

Other Adjuvants

The oxidizing composition may also contain various conventionally usedadjuvants, for instance anionic, cationic, nonionic, amphoteric orzwitterionic polymers or mixtures thereof; thickeners such ascrosslinked acrylic acid homopolymers, cellulose-based thickeners (with,for example, hydroxyethylcellulose, hydroxypropylcellulose orcarboxymethylcellulose), guar gum and derivatives thereof (for examplehydroxypropylguar), gums of microbial origin (especially xanthan gum orscleroglucan gum); sequestrants such as ethylenediaminetetraacetic orsalts thereof; fragrances; and preserving agents, or mixtures thereof.

The above adjuvants are generally present in an amount for each of themof between 0.01% and 20% by weight relative to the weight of theoxidizing composition.

Propellant Gas

As has been indicated previously, at least one of the dye and/oroxidizing compositions used in the process according to the invention isdispensed from at least one pressurized device. In other words, themixture used in the process according to the invention comprises(initially) one or more propellant gases.

It should be noted that, in the context of the invention, the propellantgas may be employed to enable the expulsion of the composition(s), butalso to facilitate or bring about their expansion.

As indicated previously, at least one of the compositions comprises atleast one propellant gas, and preferably both the compositions compriseat least one propellant gas. In other words, the gas(es) are mixed withthe composition.

As propellant gases that are suitable for use in the invention, mentionmay be made of the gases usually used in the cosmetic field, inparticular optionally halogenated volatile hydrocarbons, for examplen-butane, propane, isobutane or pentane, and halogenated derivativesthereof; carbon dioxide, nitrous oxide, dimethyl ether and nitrogen,alone or as mixtures.

Preferably, the propellant gas(es) are chosen from alkanes and inparticular from n-butane, propane and isobutane, and mixtures thereof.

The gases are under pressure, more particularly at least partially inliquid form.

In the preferred case in which each of the compositions comprises atleast one propellant gas, these gases may be identical or different fromone composition to another, whether as regards the nature of the gas(es)or as regards the respective proportions thereof if it is a case ofmixtures.

Preferably, the content of propellant gas(es) represents a contentranging from 1% to 30% by weight relative to the weight of thecomposition, and preferably from 2% to 15% by weight relative to theweight of the composition in which they are present.

Device

The mixture applied to the fibres is thus obtained from the mixing ofthe dye and oxidizing compositions described previously.

The mixture may be obtained from a single pressurized containercomprising either the oxidizing composition or the dye composition asdescribed previously, the said composition being mixed before use with acomposition (the dye composition or the oxidizing composition,respectively) obtained from a non-pressurized container such as a bottleor a tube, the mixture of the two compositions comprising at least oneglycerolated fatty alcohol and/or at least one oxyalkylenated carboxylicacid ether in acid or salified form, as described previously.

The mixture may also be obtained from a single pressurized containercomprising the oxidizing composition and the dye composition asdescribed previously in two separate pockets, the mixture of the twocompositions comprising at least one glycerolated fatty alcohol and/orat least one oxyalkylenated carboxylic acid ether in acid or salifiedform, as described previously.

Preferably, the said mixture used in the context of the invention isobtained from a device comprising:

-   -   a first container containing the dye composition described        previously, and    -   a second container containing the oxidizing composition also        described previously,    -   at least one of the containers being pressurized, and preferably        both the containers being pressurized;    -   a means for dispensing the compositions;    -   the mixture of the two compositions comprising at least one        saturated or unsaturated C₈-C₄₀ fatty alcohol comprising from 1        to 10 mol of glycerol, preferably from 1 to 5 mol of glycerol        and/or at least one oxyalkylenated carboxylic acid ether in acid        or salified form.

Preferably, a means for dispensing each composition is mounted on eachcontainer.

One or both the containers may have rigid walls and directly contain thecomposition.

As a variant, one or both the containers may have rigid walls andinclude a flexible-walled pocket which contains the composition.

According to this embodiment, either the dye composition is in a pocket,or the oxidizing composition is in a pocket, or both of them are.

According to this configuration, the composition in the pocket maycomprise no propellant gas, this gas being located in the volume definedbetween the rigid walls of the container and the pocket.

Preferably, the composition contained in the pocket comprises itselfalso at least one propellant gas.

According to another variant, the device comprises a first rigid-walledcontainer which contains one or the other of the dye or oxidizingcompositions, the first rigid-walled container including a flexiblepocket which itself contains the other of the dye or oxidizingcompositions and which constitutes a second container.

According to another variant, which is preferred, the device comprisestwo rigid-walled containers, preferably without a pocket, containing acomposition.

The device comprises a means for dispensing the compositions, the meanscomprising at least one dispensing valve mounted on the container(s).

Preferably, the means for dispensing the compositions comprises twodispensing valves, each valve being mounted on a container.

The valve(s) are in selective fluid communication with the interior ofthe container(s) via an inlet orifice of the valve, the communicationbeing established in response to the actuation of an actuating means,such as a push button.

When the device comprises a first rigid-walled container which includesa flexible pocket, only one valve is provided for dispensing the twocompositions. The valve is then equipped with two inlet orifices, one ofthe orifices being able to communicate with the interior of the pocketand the other with the volume defined between the pocket and the rigidwalls of the container.

When the containers do not include a pocket, they are equipped with adip tube for conveying the composition to the inlet orifice of thedispensing valve.

When the containers include a pocket, the valve inlet orifice opens intothe pocket.

The device may comprise at least one diffuser which caps the valve(s).According to a first variant, the device comprises a single diffuserwhich caps the two valves. According to a second variant, the devicecomprises two diffusers, each independently capping a valve.

The push button may form part of the diffuser.

The diffuser may be equipped with one or more dispensing ducts providedto convey the composition(s) to one or more dispensing orifices.

When the device comprises two diffusers, each of the diffusers isequipped with a duct for conveying the composition between the valveoutlet orifice and a dispensing orifice.

When the device comprises a single diffuser, it may be equipped with twoducts for conveying the compositions, each duct communicating with theoutlet orifice of a valve.

According to a first embodiment, the two ducts each arrive at adispensing orifice (not communicating with each other before thedispensing orifice). According to this configuration, the mixing of thecompositions does not take place until after they have been dispensed(and thus after the dispensing orifices).

According to a second embodiment, the two ducts arrive in a mixingchamber, from which a single duct is directed towards a singledispensing orifice. According to this configuration, the mixing of thecompositions takes place just before the mixture is expelled from thedevice.

Preferably, the two ducts each open directly onto a dispensing orifice.

When the device comprises two diffusers, namely when it comprises twocontainers, on each of which is mounted a valve and a diffuser specificthereto, the two containers may be free relative to each other, i.e. notintegrally attached.

As a variant, the two containers may be integrally attached, for exampleby means of an outer envelope partly covering the containers (especiallya thermoformed film or a metallic or plasticized rigid envelope), oralternatively by means of notches made in the outer wall of eachcontainer, enabling them to be fastened together.

When the device comprises a single diffuser which caps the two valves,this diffuser enables the two containers to be integrally attached. Inthis case, an outer envelope partly covering the containers may also beenvisaged.

In accordance with a particular embodiment of the invention, the devicecomprises two containers with integrally attached walls, the deviceenabling the compositions to be dispensed concomitantly, via one or,preferably, two dispensing orifices.

Preferably, according to this embodiment, the containers are rigid, adispensing valve being mounted on each of the containers, a singlediffuser capping the two valves.

Needless to say, the devices are designed such that the dye andoxidizing compositions come into contact at the time of application ofthe mixture obtained.

Mixture

Advantageously, the mixture of the dye composition and of the oxidizingcomposition, used in the process according to the invention, and whichis applied to the fibres, is preferably in the form of a foam, which isthus produced just before it is applied.

More particularly, the dye composition which is dispensed (obtained)from a pressurized container is in the form of a cream, a gel or a foam,preferably in the form of a foam.

Moreover, the oxidizing composition which is dispensed (obtained) from apressurized container is in the form of a cream, a gel or a foam,preferably in the form of a foam.

The pH of the mixture of the dye and oxidizing compositions isadvantageously between 3 and 12, preferably between 5 and 11 andpreferentially between 7 and 11, limits inclusive.

It should be noted that the dispensing valve(s), and similarly thecontent of propellant gas(es), are adapted so as to enable thecompositions to be dispensed in suitable respective proportions.

In practice, the dye composition/oxidizing composition weight ratio inthe dispensed mixture ranges from 0.25 to 4 and preferably from 0.5 to2.

Even more preferentially, this ratio is 1.

The dyeing process according to the invention consists in applying themixture thus obtained to wet or dry human keratin fibres for a timesufficient to develop the desired coloration.

According to the invention, the mixture obtained according to theprocess according to the invention is applied to keratin fibrespreferably in the form of a foam.

The dyeing process is generally performed at room temperature (between15 and 25° C.) and up to temperatures that may be as high as 60° C. to80° C.

After a leave-on time of from one minute to one hour and preferably from5 minutes to 30 minutes, the human keratin fibres are rinsed with water,and optionally washed with a shampoo and then rinsed with water.

The example that follows serves to illustrate the invention without,however, being limiting in nature.

EXAMPLE Example 1

Dye Composition (Contents Expressed in g % in Native Form):

Ingredients Concentration Polyglycerolated (2 mol) oleyl alcohol(Chimexane NC; 4 sold by the company Chimex) Polyglycerolated (4 mol)oleyl alcohol (78% in water; 7.69 Chimexane NB, sold by the companyChimex) Diethylaminopropyl laurylaminosuccinamate, sodium 5.45 salt, asan aqueous 55% solution Oleic acid 3 Oleyl alcohol 5 Oxyethylenated (2OE) oleylamine (Rhodameen O2/V 7 sold by the company Rhodia) Carboxylicacid (50% linear 70/30 C13/C15)alkyl ether 10 monoethanolamide (2 OE)(Amidet A15/LAO 55, sold by the company Kao) 96° Ethyl alcohol 5Propylene glycol 9.7 Fragrance 0.75 Hexylene glycol(2-methyl-2,4-pentanediol) 9.3 Erythorbic acid 0.12Diethylenetriaminepentaacetic acid, pentasodium salt, 2.4 as an aqueous40% solution Powdered sodium metabisulfite 0.455 Ammonium acetate 0.81-Methyl-2,5-diaminobenzene 0.151,3-Bis[(4-aminophenyl)(2-hydroxyethyl)amino-2- 0.01 propanoltetrahydrochloride 1,3-Dihydroxybenzene 0.102-Methyl-1,3-dihydroxybenzene 0.05 1-Hydroxy-3-aminobenzene 0.01 Aqueousammonia (20% concentration of ammonia) 10.2 Deionized water qs 100Oxidizing Composition (Contents Expressed in g % in Native Form):

Chemical name Concentration Mixture of cetylstearylalcohol/oxyethylenated (33 OE) 2.85 cetylstearyl alcohol (Sinnowax AOsold by the company Cognis) (50% linear 70/30 C₁₃/C₁₅)alkyl ethercarboxylic acid 0.85 monoethanolamide (2 OE) Glycerol 0.5 Tetrasodiumpyrophosphate decahydrate 0.02 Disodium tin hexahydroxide 0.04Diethylenetriaminepentaacetic acid, pentasodium salt 0.15 as an aqueous40% solution 50% hydrogen peroxide solution 12 Phosphoric acid q.s. forpH 2.2 Deionized water q.s. for 100

Each of the above compositions is conditioned in an aerosol container inthe presence of the following propellant gases, in acomposition/propellant gases weight ratio of 94/6.

-   -   Dye composition: 50% propane, 35% n-butane, 15% i-butane    -   Oxidizing composition: 25% propane, 40% n-butane, 35% i-butane

The two aerosols are integrally attached via a dispensing headincorporating the two dispensing channels deriving from the twopressurized containers, the mixing of the two compositions in a weightratio of 1/1 not taking place until immediately after exiting thedispensing head.

The resulting mixture is left on the fibres for 30 minutes at roomtemperature (25° C.).

A natural light blond shade, which covers grey hair well, is obtained.

Example 2

Dye Composition (Contents Expressed in g % in Native Form):

ingrédients Concentration Oxyethylenated (4 OE) rapeseed acid amide (at92% by 8.8 weight, Amidet N sold by the company Kao) Oxyethylenated (5OE) decyl alcohol (at 90% by weight, 7.7 Eumulgin BL 589 sold by thecompany Cognis) Glyceryl C12 alkyl ether (1.5 mol) (Chimexane NV sold 7by the company Chimex) Oleyl alcohol 1.1 Lauryl ether carboxylic acid(4.5 OE) (at 90% by weight, 5 Akypo RLM 45 CA sold by the company Kao)Monoethanolamine 3.66 Ethylenediaminetetraacetic acid 0.2 96° Ethylalcohol 8.8 Propylene glycol 6.2 Hexylene glycol 3 Dipropylene glycol 3Condensate of ethylene oxide and of propylene oxide and 2 of ethyleneoxide (MW: 14 000) (128 OE/54 OP/128 OE) (at 99.95% by weight,Synperonic PE/F 108 (flakes) sold by the company Croda)Polydimethyldiallylammonium chloride at 40% in water 0.1 (Merquat 100sold by the company Nalco) Ammonium thiolactate as an aqueous 58%solution (50% 0.8 concentration of thiolactic acid) Fragrance 0.95Erythorbic acid 0.31 1,4-Diaminobenzene 1.45N,N-Bis(2-hydroxyethyl)-p-phenylenediamine sulfate 0.30 monohydrate1,3-Dihydroxybenzene 0.75 1-Hydroxy-3-aminobenzene 0.651-β-Hydroxyethyloxy-2,4-diaminobenzene 0.35 dihydrochloride Aqueousammonia (20% concentration of ammonia) 7 Deionized water qsp 100Oxidizing Composition (Contents Expressed in g % in Native Form):

Chemical name Concentration Mixture of cetylstearylalcohol/oxyethylenated (33 OE) 2.85 cetylstearyl alcohol (Sinnowax AOsold by the company Cognis) (50% linear 70/30 C₁₃/C₁₅)alkyl ethercarboxylic acid 0.85 monoethanolamide (2 OE) Glycerol 0.5 Tetrasodiumpyrophosphate decahydrate 0.02 Disodium tin hexahydroxide 0.04Diethylenetriaminepentaacetic acid, pentasodium salt 0.15 as an aqueous40% solution 50% hydrogen peroxide solution 12 Phosphoric acid q.s. forpH 2.2 Deionized water q.s. for 100

Each of the above compositions is conditioned in an aerosol container inthe presence of the following propellant gases, in acomposition/propellant gases weight ratio of 94/6.

-   -   Dye composition: 50% propane, 35% n-butane, 15% i-butane    -   Oxidizing composition: 25% propane, 40% n-butane, 35% i-butane

The two aerosols are integrally attached via a dispensing headincorporating the two dispensing channels deriving from the twopressurized containers, the mixing of the two compositions in a weightratio of 1/1 not taking place until immediately after exiting thedispensing head.

The resulting mixture is left on the fibres for 30 minutes at roomtemperature (25° C.).

A natural dark shade, which covers grey hair well, is obtained.

The invention claimed is:
 1. A process for dyeing keratin fibercomprising: (a) preparing a cosmetic mixture by mixing: a dyecomposition comprising at least one oxidation dye precursor, and anoxidizing composition comprising at least one chemical oxidizing agent;and (b) applying said cosmetic mixture to said keratin fibers; whereinthe cosmetic mixture comprises at least one of: (i) a glycerolatedsurfactant chosen from compounds of formula (A) below:R₁O—[CH₂—CH(CH₂OH)—O]_(m)—H  (A) wherein:  R₁ is chosen from linear orbranched C₈-C₃₀ alkyl or alkenyl radicals, and  m is equal to an integerranging from 1 to 10, or (ii) an oxyalkylenated carboxylic acid etherchosen from compounds of formula (I):

wherein:  R is chosen from (C₁₂-C₁₄) alkyl, oleyl, cetyl or stearylradicals or mixtures of radicals, or nonylphenyl or octylphenylradicals,  A is chosen from a hydrogen atom an ammonium ion, an ionderived from an alkali metal or an alkaline-earth metal, or an ionderived from an organic amine,  p is equal to an integer ranging from 0to 6, and  n is equal to an integer ranging from 2 to 20, and furtherwherein at least one of the dye composition and the oxidizingcomposition is dispensed from a pressurized container.
 2. The processaccording to claim 1, wherein at least one glycerolated surfactant ispresent in the cosmetic mixture in an amount ranging from about 0.1% toabout 50% by weight, relative to the weight of the cosmetic mixture. 3.The process according to claim 1, wherein the at least oneoxyalkylenated carboxylic acid ether is present in the cosmetic mixturein an amount ranging from about 0.1% to about 40% by weight, relative tothe weight of the cosmetic mixture.
 4. The process according to claim 1,wherein the at least one oxidation dye precursor is chosen fromoxidation bases and couplers.
 5. The process according to claim 1,wherein the pressurized container comprises at least one propellant gaschosen from optionally halogenated volatile hydrocarbons and halogenatedderivatives thereof.
 6. The process according to claim 5, wherein the atleast one propellant gas is chosen from n-butane, propane, isobutene,pentane, carbon dioxide, nitrous oxide, dimethyl ether, nitrogen,compressed air, and mixtures thereof.
 7. The process according to claim1, wherein the dye composition and the oxidizing composition eachcomprise at least one propellant gas, which may be the same ordifferent, wherein the at least one propellant gas is present in anamount ranging from about 1% to about 30%, relative to the weight of thecomposition in which it is present.
 8. The process according to claim 1,wherein the at least one chemical oxidizing agent is chosen fromhydrogen peroxide, urea peroxide, alkali metal bromates orferricyanides, peroxygenated salts and peracids, and precursors thereof.9. The process according to claim 1, wherein the dye compositioncomprises at least one alkaline agent chosen from aqueous ammonia,alkanolamines, amino acids, or mixtures thereof.
 10. The processaccording to claim 9, wherein the at least one alkaline agent is presentin the dye composition in an amount ranging from about 0.01% to about30% by weight, relative to the weight of the dye composition.
 11. Theprocess according to claim 1, wherein the dye composition and/or theoxidizing composition comprises at least one additional surfactant otherthan the glycerolated surfactant, wherein the at least one additionalsurfactant is chosen from cationic, amphoteric, nonionic, and anionicsurfactants.
 12. The process according to claim 1, wherein the dyecomposition and the oxidizing composition are each in a differentpressurized container, wherein the containers are optionally integrallyattached and equipped with at least one dispensing orifices configuredto dispense the compositions concomitantly.
 13. The process according toclaim 1, wherein the cosmetic mixture, as dispensed, is in the form of afoam.
 14. A device for dispensing a cosmetic mixture for dyeing keratinfibers, said cosmetic mixture comprising: a dye composition comprisingat least one oxidation dye precursor, an oxidizing compositioncomprising at least one chemical oxidizing agent, and at least one of:(i) a glycerolated surfactant chosen from compounds of formula (A)below:R₁O—[CH₂—CH(CH₂OH)—O]_(m)—H  (A) wherein: R₁ is chosen from linear orbranched C₈-C₃₀ alkyl or alkenyl radicals, and m is equal to an integerranging from 1 to 10, or (ii) an oxyalkylenated carboxylic acid etherchosen from compounds of formula (I):

wherein: R is chosen from (C₁₂-C₁₄) alkyl, oleyl, cetyl or stearylradicals or mixtures of radicals, or nonylphenyl or octylphenylradicals, A is chosen from a hydrogen atom an ammonium ion, an ionderived from an alkali metal or an alkaline-earth metal, or an ionderived from an organic amine, p is equal to an integer ranging from 0to 6, and n is equal to an integer ranging from 2 to 20, said devicecomprising: a first container containing the dye composition comprisingat least one oxidation dye precursor, and a second container containingthe oxidizing composition comprising at least one chemical oxidizingagent, wherein at least one of the first and second containers ispressurized and equipped with a component for dispensing the cosmeticmixture of the dye and oxidizing compositions.